1. Field of the Invention
This invention relates to a manufacturing method for a multilayered ceramic body, such as a multilayer ceramic substrate, for mounting thereon semiconductor ICs and chips and for interconnecting them with each other, and to a metalized composition for the multilayered ceramic body.
2. Description of the Prior Art
The known multilayer ceramic substrate manufacturing methods are classified into three types 1: a thick film method, 2 a green sheet printing method and 3 a green sheet laminating method. Next, these methods will be described briefly. At first, the thick film method is represented by the hybrid IC, which employs thick film paste of conductors and insulators and repeatedly applies to an already sintered ceramic substrate the screen process printing and baking to thereby form patterns. This method is relatively easy to perform because the thick film paste is readily obtainable and the method itself is simple, thereby being now widely practiced. The thick film method, however, uses glass as the insulating layer and is not so much multilayered, thereby being limited to three to four layers. The screen process printing and firing are repeated for multilayering each layer to result in that a long lead time and a high manufacturing cost. Also, the use of the sintered substrate will create a defect in that the through hole processing is difficult.
Next, the green sheet printing method uses a ceramic sheet which is fabricated by the following process. A ceramic powder (e.g. alumina or beryllia as the main component) added with an organic binder, a plasticizer and a solvent, formed in slurry by use of a ball mill, and is formed in a sheet-like film (called the green sheet) by means of the doctor blade. The conductor paste uses high melting point metal, such as tungsten (W), molybdenum (Mo) or molybdenum-manganese (Mo-Mn), and the insulating layer paste uses paste using an inorganic component having the same composition as the green sheet material. In this method, the conductor paste and insulator paste are printed alternately on the green sheet to be multilayered, and after being printed and dried, the sintering is carried out at once, at which time the sintering is usually carried out under a reducing atmosphere in which the high melting point metal is not oxidized, for example, 96% alumina is sintered a temperature of 1600.degree. C. The reducing atmosphere usually contains nitrogen and some water vapor gasses including hydrogen gas of concentration of about 10% (as disclosed in, for example, "A Fabrication Technique For Multilayer Ceramic Modules", Solid State Technology 15, No. 5, P 35.about.40 (May, 1972)).
Such green sheet method is very advantageous and is expected to be widely used in the future. Its advantages are as follows: Firstly, the sintering is carried out at once after the sheet is printed and multilayered to thereby reduce manufacturing time. Secondly, the insulating layers are the same in composition as the substrate material and are sintered simultaneously so that a dense sintered body superior in thermal conductivity and airtightness is obtainable. Thirdly, the use of green sheet increases the processability, such as the through hole processing and is superior in fine printing efficiency. Fourthly, the use of metal, such as W, Mo or Mo-Mn, lowers material cost in comparison with Au or Ag/Pd series conductor material. Fifthly, the sintered body is shrunk when sintered, thereby being actually higher in fine line printing. Sixthly, adhesion strength of conductor layer is larger than that in the thick film method. The green sheet method, however, is defective in that a large design change is difficult, it is dangerous to be processed at a high temperature and to require a hydrogen atmosphere, resulting in a high fabrication cost, and the conductor is higher in electrical resistance than Au, Ag or Cu and not to be soldered, thereby requiring the surface treatment for plating Ni or Au on the surface.
The green sheet laminating method is similar to the green sheet printing method, but is different in the multilayering process of laminating a number of green sheet printed conductors and formed through holes.
This method is effective for a large number of laminations, but requires molds or jigs as many as the laminations for the through hole processing to the green sheet and is low in degree of freedom for design change, thereby having been not as popular as the green sheet printing method.
Next, paying attention to the metallized conductive material used for the ceramic substrate, the thick film method uses Au, Ag/Pd or Cu, and the green sheet method W, Mo or Mo-Mn. The Au and Ag/Pd are fired in air, but the method is expensive due to noble metals. Also, the green sheet method, which sinters the ceramic substrate at a high temperature of 1500.degree. C. or more, thereby creates a problem in that the high melting point metal, such as W, Mo, or Mo-Mn, only is usable. Hence, at present, a Cu metallized substrate has been noted which is low in conductor resistance, generates no migration phenomenon, and is good in soldering. Thus, the Cu metallized wiring substrate is already put into practical use, But, there is a drawback in the Cu metallized substrate because of using the base-metal. The reason for the above is that said base metal, when fired in air, is oxidized not to obtain the conductivity, and that in order to obtain the adhesive property, sheet resistance, and soldering property of the wiring and to eliminate decomposition of organic binder in the paste, very delicate atmosphere control of including some oxygen in the nitrogen atmosphere is required.
Furthermore, in the case where a glazed resistor and a dielectric are formed after the Cu conductor is formed, a firing atmosphere the same as the above-mentioned one is required. However, such resistor and dielectric usable in this condition are rare and the degree of freedom for selection is very little. Nevertheless, the merit of the base metal conductor material represented by Cu is attractive.
Now, in consideration of the future of the multilayer substrate, it will be ideal to use the base metal material as the conductor material and to utilize the green sheet method for the multilayer method. In other words, a base metal conductor, such as copper, is printed on the green sheet and the insulating layer is printed or laminated in multilayers so as to obtain the multilayer substrate.
However, there are some problems to be solved in order to put the base metal multilayer substrate into practical use. A first problem is created in that since the melting point of Cu, the typical base metal, is low at a temperature of 1083.degree. C., it is necessary for sintering simultaneously with the substrate material to keep the sintering temperature thereof lower than the aforesaid melting point. This is indispensable in order to satisfy requirements as to mechanical strength of sintered body, dielectric strength (or break-down voltage), moisture resistance and thermal conductivity of the substrate material. Further the performance, such as the metallizing property of the Cu, is required when multilayered. A second problem is that it may be difficult to use the binder under such sintering condition of temperature or atmosphere. In other words, the organic binder used for the sheet or the paste has the property of not decomposing in a non-oxidizing atmosphere. Unless the binder is completely decomposed and removed, the ceramic body itself remains porous, whereby not only the sintering does not proceed but also the substrate becomes blackish due to the residual carbon is merely obtained.
For the aforesaid simultaneously sintering substrate material, glass-ceramic material has generally been developed, which has been disclosed in, for example, U.S. application Ser. No. 449,564 (corresponding to Japanese Laid-Open Patent Application No. 50-119814) and U.S. Pat. Nos. 3,977,887 and 4,301,324, the decomposition and removal of the binder having been disclosed in the Japanese Laid-open Patent Application No. 55-128899.